U.S. patent number 11,453,732 [Application Number 17/063,508] was granted by the patent office on 2022-09-27 for polyethylene copolymers and products and methods thereof.
This patent grant is currently assigned to Braskem S.A.. The grantee listed for this patent is Braskem S.A.. Invention is credited to Markus Busch, Manoela Ellwanger Cangussu, Nei Sebastiao Domingues Junior, Jonas Alves Fernandes, Ashley Hanlon, Sascha Hintenlang, Hadi Mohammadi, Adriane Gomes Simanke, Mauro Alfredo Soto Oviedo.
United States Patent |
11,453,732 |
Hanlon , et al. |
September 27, 2022 |
Polyethylene copolymers and products and methods thereof
Abstract
A polymer composition may include a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (I): ##STR00001## where R.sup.1, R.sup.2 and
R.sup.3 are independently selected from a group consisting of
hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,
substituted alkoxy, alkenyl, substituted alkenyl, alkynyl,
substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles; and Y
and Z are independently selected from a group consisting of O,
(CR.sup.5aR.sup.5b), (CHR.sup.6a)--R.sup.6b, phenylene,
CH--OR.sup.7, and NR.sup.8, wherein R.sup.5a, R.sup.5b, R.sup.6a,
R.sup.6b, and R.sup.8 are independently selected from a group
consisting of hydrogen, halogen, CH.sub.2, and alkyl, and wherein
R.sup.7 is independently selected from a group consisting of
hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether;
Si(R.sup.9).sub.3, wherein R.sup.9 is independently selected from a
group consisting of hydrogen, halogen, and alkyl; and
(C.dbd.O)--R.sup.10, wherein R.sup.10 is an alkyl; and R.sup.4 is
independently selected from a group consisting of halogen,
hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles, where the polymer composition has a
number average molecular weight (M.sub.n) ranging from 5 kDa to
10000 kDa obtained by GPC.
Inventors: |
Hanlon; Ashley (Sao Paulo,
BR), Fernandes; Jonas Alves (Sao Paulo,
BR), Soto Oviedo; Mauro Alfredo (Sao Paulo,
BR), Mohammadi; Hadi (Sao Paulo, BR),
Domingues Junior; Nei Sebastiao (Sao Paulo, BR),
Simanke; Adriane Gomes (Sao Paulo, BR), Cangussu;
Manoela Ellwanger (Sao Paulo, BR), Busch; Markus
(Sao Paulo, BR), Hintenlang; Sascha (Sao Paulo,
BR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Braskem S.A. |
Camacari |
N/A |
BR |
|
|
Assignee: |
Braskem S.A. (Camacari,
BR)
|
Family
ID: |
1000006584055 |
Appl.
No.: |
17/063,508 |
Filed: |
October 5, 2020 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
|
US 20210102015 A1 |
Apr 8, 2021 |
|
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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62910620 |
Oct 4, 2019 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F
210/02 (20130101) |
Current International
Class: |
C08F
210/02 (20060101); C08F 2/04 (20060101) |
Field of
Search: |
;526/279,316 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1433836 |
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Jun 2004 |
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EP |
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2514803 |
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Oct 2012 |
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EP |
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4783209 |
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Sep 2011 |
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JP |
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2010105979 |
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Sep 2010 |
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WO |
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Other References
International Search Report issued in International Application No.
PCT/IB2020/020059, dated Dec. 17, 2020 (5 pages). cited by
applicant .
Written Opinion issued in International Application No.
PCT/IB2020/020059, dated Dec. 17, 2020 (7 pages). cited by
applicant .
International Search Report issued in International Application No.
PCT/IB2020/020058, dated Feb. 24, 2021 (10 pages). cited by
applicant .
Written Opinion issued in International Application No.
PCT/IB2020/020058, dated Feb. 24, 2021 (10 pages). cited by
applicant.
|
Primary Examiner: Teskin; Fred M
Attorney, Agent or Firm: Osha Bergman Watanabe & Burton
LLP
Claims
What is claimed:
1. A polymer composition, comprising: a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (I): ##STR00013## where R.sup.1, R.sup.2 and
R.sup.3 are independently selected from a group consisting of
hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,
substituted alkoxy, alkenyl, substituted alkenyl, alkynyl,
substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles; and Y
and Z are independently selected from a group consisting of O,
(CR.sup.5aR.sup.5b), (CHR.sup.6a)--R.sup.6b, phenylene, and
CH--OR.sup.7, and NR.sup.8, wherein R.sup.5a, R.sup.5b, R.sup.6a,
R.sup.6b, and R.sup.8 are independently selected from a group
consisting of hydrogen, halogen, CH.sub.2, and alkyl, and wherein
R.sup.7 is independently selected from a group consisting of
hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether;
Si(R.sup.9).sub.3, wherein R.sup.9 is independently selected from a
group consisting of hydrogen, halogen, and alkyl; and
(C.dbd.O)--R.sup.10, wherein R.sup.10 is an alkyl; and R.sup.4 is
independently selected from a group consisting of halogen,
hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles; where the polymer composition has a
number average molecular weight (M.sub.n) ranging from 5 kDa to
10000 kDa, and a molecular weight distrution ranging from 1.5 to
60, obtained by GPC.
2. The polymer composition of claim 1, wherein Y or Z is
CH--OR.sup.7, wherein R.sup.7 is selected from a group consisting
of hydrogen; alkyl; Si(R.sup.9).sub.3, wherein R.sup.9 is selected
from a group consisting of hydrogen, halogen, and alkyl; linear
ether; cyclic ether; and (C.dbd.O)--R.sup.10, wherein R.sup.10 is
an alkyl.
3. The polymer composition of claim 1, wherein the one or more
vinyl carbonyl monomers comprise a mixture of isomers.
4. The polymer composition of claim 1, wherein Y is O.
5. The polymer composition of claim 1, wherein R.sup.1, R.sup.2,
and R.sup.3 are hydrogen.
6. The polymer composition of claim 1, wherein the general
structure of Z is C(R.sup.5aR.sup.5b), and wherein R.sup.5a and
R.sup.5b are each independently selected from a group consisting of
hydrogen, halogen, and alkyl.
7. The polymer composition of claim 1, wherein the polymer
composition further comprises one or more diene monomers.
8. The polymer composition of claim 7, wherein the one or more
diene monomers are present at a percent by weight of the polymer
composition (wt %) ranging from greater than 0.01 wt % to 50 wt %
measured by .sup.1H NMR and/or .sup.13C NMR.
9. The polymer composition of claim 7, wherein the one or more
diene monomers are selected from the group consisting of
dicyclopentadiene, 1,3-pentadiene and combinations thereof.
10. The polymer composition of claim 1, wherein the one or more
vinyl carbonyl monomers are present at a percent by weight of the
polymer composition (wt %) ranging from greater than 0.01 wt % to
90 wt % measured by .sup.1H NMR and/or .sup.13C NMR.
11. The polymer composition of claim 1, wherein the crystallinity
of the polymer composition is in the range of 0.1% to 80% measured
by DSC, according to ASTM D3418, or WAXD.
12. The polymer composition of claim 1, wherein the glass
transition temperature of the polymer composition is in the range
of -70.degree. C. to 100.degree. C. measured by DMA or DSC.
13. The polymer composition of claim 1, wherein the melting
temperature of the polymer composition, according to ASTM D3418, is
in the range of 0.degree. C. to 150.degree. C. measured by DSC.
14. The polymer composition of claim 1, wherein the crystallization
temperature of the polymer composition, according to ASTM D3418, is
in the range of 0.degree. C. to 150.degree. C. measured by DSC.
15. The polymer composition of claim 1, wherein the long chain
branching frequency ranges from 0 to 10, as measured by GPC.
16. The polymer composition of claim 1, wherein the long chain
branching content ranges from 0 to 10, as measured by
.sup.13CNMR.
17. The polymer composition of claim 1, wherein the polymer has a
heat flow versus temperature curve, measured by thermal
fractionation by successive self-nucleation and annealing with
10.degree. C. steps, that has 0 to 20 minimums.
18. The polymer composition of 17, wherein the minimums are in a
temperature range of 0 to 150.degree. C.
19. The polymer composition of claim 1, wherein a ratio of a first
weight loss, between 250 to 400.degree. C., relative to a total
comonomer content, ranges from 0 to 2.
20. The polymer composition of claim 1, wherein the polymer has a
storage modulus at 0.degree. C. ranging from 0.1 MPa to 50 GPa.
21. The polymer composition of claim 1, wherein the polymer has 1
to 2 relaxation maximums in a tan .delta. versus temperature plot
between -75 to 75.degree. C.
22. The polymer composition of claim 21, wherein T.sub..alpha.
varies between -75 and 75.degree. C.
23. The polymer composition of claim 22, wherein T.sub..beta.
varies between -75 and 50.degree. C.
24. The polymer composition of claim 1, wherein the hardness of the
polymer composition as determined according to ASTMD2240 is in the
range of 35 to 90 Shore A.
25. The polymer composition of claim 1, wherein the hardness of the
polymer composition as determined according to ASTMD2240 is in the
range of 20 to 60 Shore D.
26. The polymer composition of claim 1, wherein the MFR according
to ASTM D1238 at 190.degree. C./2.16 kg is in the range of 0.01
g/10 min to 1000 g/10 min.
27. The polymer composition of claim 1, wherein the density
according to ASTM D1505/D792 is in the range of 0.85 g/cm.sup.3 to
1.3 g/cm.sup.3.
28. The polymer composition of claim 1, wherein the bio-based
carbon content according to ASTM D6866-18 is in the range of 1% to
100%.
29. The polymer composition of claim 1, wherein the polymer
composition is prepared by solution phase polymerization.
30. The polymer composition of claim 1, wherein the polymer
composition is prepared by low pressure polymerization.
31. The polymer composition of claim 1, wherein the polymer
composition is prepared by high-pressure polymerization.
32. The polymer composition of claim 1, wherein the polymer is
produced with the addition of one or more initiators for
free-radical polymerization added at a percent by weight of the
total composition ranging from 10.sup.-7 wt % to 5 wt %.
33. The polymer composition of claim 1, wherein the one or more
vinyl carbonyl monomers have the general structure (II):
##STR00014## wherein R.sup.11, R.sup.12, and R.sup.13 have a
combined carbon number in the range of C3 to C20 and the polymer
composition has a number average molecular weight (M.sub.n) ranging
from 5 kDa to 10000 kDa obtained by GPC.
34. The polymer composition of claim 33, wherein the one or more
vinyl carbonyl monomers have the general structure (III):
##STR00015## wherein R.sup.16 and R.sup.17 have a combined carbon
number of 6 or 7 and the polymer composition has a number average
molecular weight (M.sub.n) ranging from 5 kDa to 10000 kDa obtained
by GPC.
35. The polymer composition of claim 1, wherein the polymer
composition further comprises a vinyl acetate monomer.
36. The polymer composition of claim 35, wherein the polymer
composition comprises a vinyl acetate monomer content at a percent
by weight (wt %) of the polymer composition ranging from greater
than 0.01 wt % to 90 wt % measured by .sup.1H NMR and/or .sup.13C
NMR.
37. A polymer composition, comprising: a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (I): ##STR00016## where R.sup.1, R.sup.2 and
R.sup.3 are independently selected from a group consisting of
hydrogen, halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,
substituted alkoxy, alkenyl, substituted alkenyl, alkynyl,
substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles; and Y
and Z are independently selected from a group consisting of O,
(CR.sup.5aR.sup.5b), (CHR.sup.6a)--R.sup.6b, phenylene, and
CH--OR.sup.7, and NR.sup.8, wherein R.sup.5a, R.sup.5b, R.sup.6a,
R.sup.6b, and R.sup.8 are independently selected from a group
consisting of hydrogen, halogen, CH.sub.2, and alkyl, and wherein
R.sup.7 is independently selected from a group consisting of
hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether;
Si(R.sup.9).sub.3, wherein R.sup.9 is independently selected from a
group consisting of hydrogen, halogen, and alkyl; and
(C.dbd.O)--R.sup.10, wherein R.sup.10 is an alkyl; and R.sup.4 is
independently selected from a group consisting of halogen,
hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles wherein when Y is O, the combined carbon
count of Z and R.sup.4 is less than 8 or more than 9; and wherein
the polymer composition has a number average molecular weight
(M.sub.n) ranging from 5 kDa to 10000 kDa, and a molecular weight
distribution ranging from 1.5 to 60, obtained by GPC.
38. A polymer composition, comprising: a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (IV): ##STR00017## wherein R.sup.14 and R.sup.15
are independently selected from the group consisting of hydrogen,
halogen, hydroxyl, alkyl, substituted alkyl, alkoxy, substituted
alkoxy, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, substituted
heterocycles, and Si(R.sup.9).sub.3, wherein R.sup.9 is selected
from a group consisting of hydrogen, halogen, and alkyl; linear
ether; cyclic ether.
39. An article prepared from the polymer composition of claim
1.
40. The article of claim 39, wherein the article is a seal, a hose,
a footwear insole, a footwear midsole, a footwear outsole, an
automotive bumper, sealing systems, hot melt adhesives, films,
conveyor belts, sportive articles, rotomolded articles, primers,
linings, industrial flooring, and acoustic insulation.
41. A method of preparing a polymer composition, the method
comprising: adding to a reactor ethylene, and one or more vinyl
carbonyl monomers having the general structure: ##STR00018## where
R.sup.1, R.sup.2 and R.sup.3 are independently selected from a
group consisting of hydrogen, halogen, hydroxyl, alkyl, substituted
alkyl, alkoxy, substituted alkoxy, alkenyl, substituted alkenyl,
alkynyl, substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles; and Y
and Z are independently selected from a group consisting of O,
(CR.sup.5aR.sup.5b), (CHR.sub.6a)--R.sup.6b, phenylene, and
CH--OR.sup.7, and NR.sup.8, wherein R.sup.5a, R.sup.5b, R.sup.6a,
R.sup.6b, and R.sup.8 are independently selected from a group
consisting of hydrogen, halogen, CH.sub.2, and alkyl, and wherein
R.sup.7 is independently selected from a group consisting of
hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether;
Si(R.sup.9).sub.3, wherein R.sup.9 is independently selected from a
group consisting of hydrogen, halogen, and alkyl; and
(C.dbd.O)--R.sup.10, wherein R.sup.10 is an alkyl; and R.sup.4 is
independently selected from a group consisting of halogen,
hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles; and reacting the ethylene and one or more
vinyl carbonyl monomers to produce the polymer composition with a
number average molecular weight (M.sub.n) ranging from 5 kDa to
10000 kDa, and a molecular weight distribution ranging from 1.5 to
60, obtained by GPC.
42. The method of any claim 41, wherein the one or more vinyl
carbonyl monomers comprise vinyl acetate and one or more
comonomers.
43. The method of claim 41, wherein the method further comprises
adding one or more diene comonomer to the reactor.
44. The method of claim 41, wherein the reactor is a high-pressure
reactor.
45. The method of claim 41, wherein the pressure applied in the
reactor is 40 to 4,000 bar.
46. The method of claim 41, wherein the temperature in the reactor
during the reaction is 50.degree. C. to 350.degree. C.
Description
BACKGROUND
The manufacture of polyolefin materials such as polyethylene (PE)
and polypropylene (PP) are the highest production volume of a
synthetic polymer ever invented. The success of these materials
were greatly achieved due to its low production cost, energy
efficiency, low greenhouse gas emission, versatility to produce a
wide range of polymers with different properties, and high polymer
processability. The wide range of articles produced with polyolefin
materials includes films, molded products, foams, pipes, textiles,
and the like. These products also have the attractiveness to be
recycled by pyrolysis to gas and oil or by incineration to energy.
The physical and chemical properties of polyolefin compositions may
exhibit varied responses depending on a number of factors such as
molecular weight, distribution of molecular weights, content,
nature and distribution of comonomer (or comonomers), the presence
of short and/or long chain-branches and its distribution, thermal
and shear history, and the like, which define their applicability
in certain applications. To increase their utilization, polyolefins
may be formulated as random and block copolymers with a number of
possible comonomers, and as mixtures with a number of potential
additives.
SUMMARY
This summary is provided to introduce a selection of concepts that
are further described below in the detailed description. This
summary is not intended to identify key or essential features of
the claimed subject matter, nor is it intended to be used as an aid
in limiting the scope of the claimed subject matter.
In one aspect, embodiments disclosed herein relate to a polymer
composition, that includes a polymer produced from ethylene, and
one or more vinyl carbonyl monomers having the general structure
(I):
##STR00002## where R.sup.1, R.sup.2 and R.sup.3 are independently
selected from a group consisting of hydrogen, halogen, hydroxyl,
alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl,
substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,
(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles; and Y and Z are independently selected
from a group consisting of O, (CR.sup.5aR.sup.5b),
(CHR.sup.6a)--R.sup.6b, phenylene, CH--OR.sup.7, and NR.sup.8,
wherein R.sup.5a, R.sup.5b, R.sup.6a, R.sup.6b, and R.sup.8 are
independently selected from a group consisting of hydrogen,
halogen, CH.sub.2, and alkyl, and wherein R.sup.7 is independently
selected from a group consisting of hydrogen; halogen; hydroxyl;
alkyl; linear ether; cyclic ether; Si(R.sup.9).sub.3, wherein
R.sup.9 is independently selected from a group consisting of
hydrogen, halogen, and alkyl; and (C.dbd.O)--R.sup.10, wherein
R.sup.10 is an alkyl; and R.sup.4 is independently selected from a
group consisting of halogen, hydroxyl, alkyl, substituted alkyl,
alkoxy, substituted alkoxy, alkenyl, substituted alkenyl, alkynyl,
substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles, and
where the polymer composition has a number average molecular weight
(M.sub.n) ranging from 5 kDa to 10000 kDa obtained by gel
permeation chromatography (GPC).
In one aspect, embodiments disclosed herein relate to a polymer
composition, that includes a polymer produced from ethylene, and
one or more vinyl carbonyl monomers having the general structure
(I):
##STR00003## where R.sup.1, R.sup.2 and R.sup.3 are independently
selected from a group consisting of hydrogen, halogen, hydroxyl,
alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl,
substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,
(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles; and Y and Z are independently selected
from a group consisting of O, (CR.sup.5aR.sup.5b),
(CHR.sup.6a)--R.sup.6b, phenylene, CH--OR.sup.7, and NR.sup.8,
wherein R.sup.5a, R.sup.5b, R.sup.6a, and R.sup.8 are independently
selected from a group consisting of hydrogen, halogen, CH.sub.2,
and alkyl, and wherein R.sup.7 is independently selected from a
group consisting of hydrogen; halogen; hydroxyl; alkyl; linear
ether; cyclic ether; Si(R.sup.9).sub.3, wherein R.sup.9 is
independently selected from a group consisting of hydrogen,
halogen, and alkyl; and (C.dbd.O)--R.sup.10, wherein R.sup.10 is an
alkyl; and R.sup.4 is independently selected from a group
consisting of halogen, hydroxyl, alkyl, substituted alkyl, alkoxy,
substituted alkoxy, alkenyl, substituted alkenyl, alkynyl,
substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles, and
wherein when Y is O, the combined carbon count of Z and R.sup.4 is
less than 8 or more than 9.
In yet another aspect, embodiments disclosed herein relate to a
polymer composition, that includes a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (II):
##STR00004## wherein R.sup.11, R.sup.12, and R.sup.13 have a
combined carbon number in the range of C3 to C20 and the polymer
composition has a number average molecular weight (M.sub.n) ranging
from 5 kDa to 10000 kDa obtained by GPC.
In yet another aspect, embodiment disclosed herein relate to a
polymer composition, that includes: a polymer produced from
ethylene, and one or more vinyl carbonyl monomers having the
general structure (IV):
##STR00005## wherein R.sup.14 and R.sup.15 are independently
selected from the group consisting of hydrogen, halogen, hydroxyl,
alkyl, substituted alkyl, alkoxy, substituted alkoxy, alkenyl,
substituted alkenyl, alkynyl, substituted alkynyl, aralkyl,
(heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, substituted
heterocycles, and Si(R.sup.9).sub.3, wherein R.sup.9 is selected
from a group consisting of hydrogen, halogen, and alkyl; linear
ether; cyclic ether.
In yet another aspect, embodiments disclosed herein relate to an
article prepared from a polymer composition having the
above-described features.
In yet another aspect, embodiments disclosed herein relate to a
method of preparing a polymer composition that includes adding to a
reactor ethylene and one or more vinyl carbonyl monomers having the
general structural formulae (I)-(IV) discussed above.
Other aspects and advantages of the claimed subject matter will be
apparent from the following description and the appended
claims.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows .sup.13C NMR spectra for a number of samples in
accordance with embodiments of the present disclosure.
FIG. 2 shows .sup.1H NMR spectra for a number of samples in
accordance with embodiments of the present disclosure.
FIG. 3 shows .sup.13C NMR spectra for a number of samples in
accordance with embodiments of the present disclosure.
FIG. 4 shows .sup.1H NMR spectra for a number of samples in
accordance with embodiments of the present disclosure.
FIG. 5 is a graphical depiction of viscometer gel permeation
chromatography (GPC) chromatograph obtained for a number of samples
in accordance with embodiments of the present disclosure.
FIGS. 6A-6C are graphical depictions of a two-dimensional liquid
chromatography (2D-LC) chromatographs for a number of samples in
accordance with embodiments of the present disclosure.
FIGS. 7A-7C is a graphical depiction of a differential scanning
calorimeter (DSC) spectra for a number of samples in accordance
with embodiments of the present disclosure.
FIGS. 8A-8B are graphical depictions of a dynamic mechanical
analysis (DMA) results for a number of samples in accordance with
embodiments of the present disclosure.
FIGS. 9A-9B are graphical depictions of a thermal gravimetric
analysis (TGA) thermogram for a number of samples in accordance
with embodiments of the present disclosure.
FIGS. 10A-10B are graphical depictions of a successive
self-nucleation and annealing (SSA) results for a number of samples
in accordance with embodiments of the present disclosure.
DETAILED DESCRIPTION
In one aspect, embodiments disclosed herein relate to polymer
compositions containing copolymers prepared from ethylene and one
or more vinyl carbonyl and/or diene monomers. In one or more
embodiments, polymer compositions may be prepared from a reaction
of ethylene and one or more branched vinyl esters and/or diene
monomers that modify various properties of the formed copolymer
including crystallinity, hardness, melt temperature, glass
transition temperature, among others.
Polymer compositions in accordance with the present disclosure may
include copolymers incorporating various ratios of ethylene and one
or more vinyl esters and/or diene monomers, including one or more
branched vinyl esters. In some embodiments, polymer compositions
may be prepared by reacting ethylene and a branched vinyl ester in
the presence of additional comonomers and one or more radical
initiators to form a copolymer. In other embodiments, terpolymers
may be prepared by reacting ethylene with a first comonomer to form
a polymer resin or prepolymer, which is then reacted with a second
comonomer to prepare the final polymer composition, wherein the
first and the second comonomer can be added in the same reactor or
in different reactors. In one or more embodiments, copolymers may
be prepared by reacting ethylene and one or more comonomers at one
or more polymerization reaction stages to obtain various repeat
unit microstructures. In one or more embodiments, the polymer
compositions may include polymers generated from monomers derived
from petroleum and/or renewable sources.
Vinyl Carbonyl Monomers
In one or more embodiments, vinyl carbonyl monomers may be
described by the general structure (I):
##STR00006##
where R.sup.1, R.sup.2 and R.sup.3 are independently selected from
a group consisting of hydrogen, halogen, hydroxyl, alkyl,
substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted
alkenyl, alkynyl, substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, and substituted heterocycles; and Y
and Z are independently selected from a group consisting of O,
(CR.sup.5aR.sup.5b), (CHR.sup.6a)--R.sup.6b, phenylene,
CH--OR.sup.7, and NR.sup.8, wherein R.sup.5a, R.sup.5b, R.sup.6a,
R.sup.6b, and R.sup.8 are independently selected from a group
consisting of hydrogen, halogen, CH.sub.2, and alkyl, and wherein
R.sup.7 is independently selected from a group consisting of
hydrogen; halogen; hydroxyl; alkyl; linear ether; cyclic ether;
Si(R.sup.9).sub.3, wherein R.sup.9 is independently selected from a
group consisting of hydrogen, halogen, and alkyl; and
(C.dbd.O)--R.sup.10, wherein R.sup.10 is an alkyl; and R.sup.4 is
independently selected from a group consisting of halogen,
hydroxyl, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
alkenyl, substituted alkenyl, alkynyl, substituted alkynyl,
aralkyl, (heterocyclo)alkyl, (heteroaryl)alkyl, (amino)alkyl,
(alkylamino)alkyl, (dialkylamino)alkyl, carboxamino(alkyl),
(cyano)alkyl, alkoxyalkyl, hydroxyalkyl, heteroalkyl, substituted
cycloalkyl, substituted cycloalkoxy, substituted aryl, and
substituted heterocycles. In one or more embodiments, the number of
carbon atoms within Z and R.sup.4 may range from a lower limit of
2, 3, or 4 and an upper limit of 12, 16, 20, or 24, where any lower
limit can be used in combination with any upper limit. In one or
more embodiments, the polymer compositions may include polymers
generated from monomers derived from petroleum and/or renewable
sources. In some embodiments, polymer compositions may include two
or more vinyl carbonyl monomers, including mixtures of isomers.
In one or more embodiments, vinyl carbonyl monomers may include
vinyl esters prepared from vinyl alcohol and a carboxylic acid,
such as vinyl acetate, vinyl propanoate, vinyl butanoate, vinyl
pentanoate, vinyl hexanoate, vinyl 2-methyl butanoate, vinyl
3-ethylpentanoate, vinyl 3-ethylhexanoate, and the like. In one or
more embodiments, when Y is O in formula (I) above, Z and R.sup.4
may be selected from the above species to have a combined carbon
count of less than 8 or more than 9 (in particular, to avoid
resulting in neodecanoate and/or neononoate groups) when the
M.sub.n is less than 5 kDa. In one or more embodiments, the polymer
compositions may include polymers generated from monomers derived
from petroleum and/or renewable sources.
In one or more embodiments, vinyl carbonyl monomers may include
branched vinyl esters, which may include branched vinyl esters
generated from isomeric mixtures of branched alkyl acids. Branched
vinyl esters in accordance with the present disclosure may have the
general chemical formula (II):
##STR00007## where R.sup.11, R.sup.12, and R.sup.13 have a combined
carbon number in the range of C3 to C20. In some embodiments,
R.sup.11, R.sup.12, and R.sup.13 may all be alkyl chains having
varying degrees of branching in some embodiments, or a subset of
R.sup.11, R.sup.12, and R.sup.13 may be independently selected from
a group consisting of hydrogen, alkyl, or aryl in some
embodiments.
In one or more embodiments, the vinyl carbonyl monomers may include
branched vinyl esters having the general chemical formula
(III):
##STR00008## wherein R.sup.16 and R.sup.17 have a combined carbon
number of 6 or 7 and the polymer composition has a number average
molecular weight (Mn) ranging from 5 kDa to 1000 kDa obtained by
GPC. In one or more embodiments, R.sup.16 and R.sup.17 may have a
combined carbon number of less than 6 or greater than 7, and the
polymer composition may have an M.sub.n up to 2000 kDa or 10000
kDa. That is, when the M.sub.n is less than 5 kDa, R.sup.16 and
R.sup.17 may have a combined carbon number of less than 6 or
greater than 7, but if the M.sub.n is greater than 5 kDa, R.sup.16
and R.sup.17 may include a combined carbon number of 6 or 7.
Examples of branched vinyl esters may include monomers having the
chemical structures, including derivatives thereof:
##STR00009## In one or more embodiments, the polymer compositions
may include polymers generated from monomers derived from petroleum
and/or renewable sources.
In one or more embodiments, branched vinyl esters may include
monomers and comonomer mixtures containing vinyl esters of
neononanoic acid, neodecanoic acid, and the like. In some
embodiments, branched vinyl esters may include Versatic.TM. acid
series tertiary carboxylic acids, including Versatic.TM. acid EH,
Versatic.TM. acid 9 and Versatic.TM. acid 10 prepared by Koch
synthesis, commercially available from Hexion.TM. chemicals. In one
or more embodiments, the polymer compositions may include polymers
generated from monomers derived from petroleum and/or renewable
sources.
In one or more embodiments, vinyl carbonyl monomers may have the
general chemical formula (IV):
##STR00010## where R.sup.14 and R.sup.15 are independently selected
from the group consisting of hydrogen, halogen, hydroxyl, alkyl,
substituted alkyl, alkoxy, substituted alkoxy, alkenyl, substituted
alkenyl, alkynyl, substituted alkynyl, aralkyl, (heterocyclo)alkyl,
(heteroaryl)alkyl, (amino)alkyl, (alkylamino)alkyl,
(dialkylamino)alkyl, carboxamino(alkyl), (cyano)alkyl, alkoxyalkyl,
hydroxyalkyl, heteroalkyl, substituted cycloalkyl, substituted
cycloalkoxy, substituted aryl, substituted heterocycles, and
Si(R.sup.9).sub.3, wherein R.sup.9 is selected from a group
consisting of hydrogen, halogen, and alkyl; linear ether; cyclic
ether. In one or more embodiments vinyl carbonyl monomers may
include alkyl vinyl glycolates such as methyl vinyl glycolate,
ethyl vinyl glycolate, and the like.
Examples of other vinyl carbonyl monomers according to formula (I)
and (IV) also include monomers having the chemical strucures,
including derivatives thereof:
##STR00011##
Diene Monomers
In one or more embodiments, the polymer compositions may optionally
include diene monomers with the ethylene and one or more vinyl
carbonyl monomers discussed above. In some embodiments, diene
monomers may have the chemical structures as presented below,
including derivatives thereof:
##STR00012## to modify various polymer properties.
Polymer compositions in accordance with the present disclosure may
include a percent by weight of ethylene measured by proton nuclear
magnetic resonance (.sup.1H NMR) and Carbon 13 nuclear magnetic
resonance (.sup.13C NMR) that ranges from a lower limit selected
from one of 0.1 wt %, 0.5 wt %, 1 wt %, and 5 wt %, to an upper
limit selected from one of 90 wt %, 95 wt %, 99.9 wt %, and 99.99
wt %, where any lower limit may be paired with any upper limit.
In some embodiments, polymer compositions in accordance with the
present disclosure may optionally include a percent by weight of
vinyl acetate measured by .sup.1H NMR and .sup.13C NMR that ranges
from a lower limit selected from one of 0.01 wt %, 0.1 wt %, 0.5 wt
%, 1 wt %, 5 wt %, 10 wt %, 20 wt % and 30 wt % to an upper limit
selected from 60 wt %, 70 wt %, 80 wt % and 90 wt % where any lower
limit may be paired with any upper limit.
Polymer compositions in accordance with the present disclosure may
include a percent by weight of vinyl carbonyl monomer (other than
vinyl acetate) measured by .sup.1H NMR and .sup.13C NMR that ranges
from a lower limit selected from one of 0.01 wt %, 0.1 wt %, 0.5 wt
%, 1 wt %, 5 wt %, 10 wt %, 20 wt % and 30 wt % to an upper limit
selected from 60 wt %, 70 wt %, 80 wt % and 90 wt % where any lower
limit may be paired with any upper limit.
Polymer compositions in accordance with the present disclosure may
optionally include a percent by weight of diene monomer measured by
.sup.1H NMR and .sup.13C NMR that ranges from a lower limit
selected from one of 0.01 wt %, 0.1 wt %, 0.5 wt %, 1 wt %, 5 wt %,
10wt %, 15 wt % and 20 wt % to an upper limit selected from 30 wt
%, 35 wt %, 40 wt % and 50 wt % where any lower limit may be paired
with any upper limit.
Polymer compositions in accordance with the present disclosure may
have a number average molecular weight (M.sub.n) in kilodaltons
(kDa) measured by gel permeation chromatography (GPC) of the
polymer composition ranges from a lower limit selected from one of
1 kDa, 5 kDa, 10 kDa, 20 kDa, and 40 kDa to an upper limit selected
from one of 100 kDa, 300 kDa, 500 kDa, 1000 kDa, 2000 kDa, 5000
kDa, or 10000 kDa where any lower limit may be paired with any
upper limit.
Polymer compositions in accordance with the present disclosure may
have a weight average molecular weight (M.sub.w) in kilodaltons
(kDa) measured by GPC of the polymer composition ranges from a
lower limit selected from one of 1 kDa, 5 kDa, 10 kDa, 15 kDa and
20 kDa to an upper limit selected from one of 40 kDa, 50 kDa, 100
kDa, 200 kDa, 300 kDa, 500 kDa, 1000 kDa, 5000 kDa, 10000 kDa and
20000 kDa where any lower limit may be paired with any upper
limit.
Polymer compositions in accordance with the present disclosure may
have a molecular weight distribution (MWD, obtained from the ratio
between M.sub.w and M.sub.n) measured by GPC that has a lower limit
of any of 1, 2, 5, or 10, and an upper limit of any of 20, 30, 40,
50, or 60, where any lower limit may be paired with any upper
limit.
Initiators for Free-Radical Polymerization
Polymer compositions in accordance with the present disclosure may
include one or more initiators for radical polymerization capable
of generating free radicals that initiate chain polymerization of
comonomers and prepolymers in a reactant mixture. In one or more
embodiments, radical initiators may include chemical species that
degrade to release free radicals spontaneously or under stimulation
by temperature, pH, or other trigger.
In one or more embodiments, radical initiators may include
peroxides and bifunctional peroxides such as benzoyl peroxide;
dicumyl peroxide; di-tert-butyl peroxide; tert-butyl cumyl
peroxide; t-butyl-peroxy-2-ethyl-hexanoate; tert-butyl
peroxypivalate; tertiary butyl peroxyneodecanoate;
t-butyl-peroxy-benzoate; t-butyl-peroxy-2-ethyl-hexanoate;
tert-butyl 3,5,5-trimethylhexanoate peroxide; tert-butyl
peroxybenzoate; 2-ethylhexyl carbonate tert-butyl peroxide;
2,5-dimethyl-2,5-di (tert-butylperoxide) hexane; 1,1-di
(tert-butylperoxide)-3,3,5-trimethylcyclohexane;
2,5-dimethyl-2,5-di(tert-butylperoxide) hexyne-3;
3,3,5,7,7-pentamethyl-1,2,4-trioxepane; butyl 4,4-di
(tert-butylperoxide) valerate; di (2,4-dichlorobenzoyl) peroxide;
di(4-methylbenzoyl) peroxide; peroxide
di(tert-butylperoxyisopropyl) benzene; and the like.
Radical initiators may also include benzoyl peroxide,
2,5-di(cumylperoxy)-2,5-dimethyl hexane,
2,5-di(cumylperoxy)-2,5-dimethyl
hexyne-3,4-methyl-4-(t-butylperoxy)-2-pentanol,
4-methyl-4-(t-amylperoxy)-2-pentano1,4-methyl-4-(cumylperoxy)-2-pentanol,
4-methyl-4-(t-butylperoxy)-2-pentanone,
4-methyl-4-(t-amylperoxy)-2-pentanone,
4-methyl-4-(cumylperoxy)-2-pentanone,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di(t-amylperoxy)hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,
2,5-dimethyl-2,5-di(t-amylperoxy)hexyne-3,
2,5-dimethyl-2-t-butylperoxy-5-hydroperoxyhexane,
2,5-dimethyl-2-cumylperoxy-5-hydroperoxy hexane,
2,5-dimethyl-2-t-amylperoxy-5-hydroperoxyhexane, m/p-alpha,
alpha-di[(t-butylperoxy)isopropyl]benzene,
1,3,5-tris(t-butylperoxyisopropyl)benzene,
1,3,5-tris(t-amylperoxyisopropyl)benzene,
1,3,5-tris(cumylperoxyisopropyl)benzene,
di[1,3-dimethyl-3-(t-butylperoxy)butyl]carbonate, di[1,3
-dimethyl-3-(t-amylperoxy) butyl]carbonate,
di[1,3-dimethyl-3-(cumylperoxy)butyl]carbonate, di-t-amyl peroxide,
t-amyl cumyl peroxide, t-butyl-isopropenylcumyl peroxide,
2,4,6-tri(butylperoxy)-s-triazine,
1,3,5-tri[1-(t-butylperoxy)-1-methylethyl]benzene,
1,3,5-tri-[(t-butylperoxy)-isopropyl]benzene,
1,3-dimethyl-3-(t-butylperoxy)butanol,
1,3-dimethyl-3-(t-amylperoxy)butanol,
di(2-phenoxyethyl)peroxydicarbonate,
di(4-t-butylcyclohexyl)peroxydicarbonate, dimyristyl
peroxydicarbonate, dibenzyl peroxydicarbonate,
di(isobomyl)peroxydicarbonate, 3-cumylperoxy-1,3-dimethylbutyl
methacrylate, 3-t-butylperoxy-1,3-dimethylbutyl methacrylate,
3-t-amylperoxy-1,3-dimethylbutylmethacrylate,
tri(1,3-dimethyl-3-t-butylperoxy butyloxy)vinyl silane,
1,3-dimethyl-3-(t-butylperoxy)butyl
N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,
1,3-dimethyl-3-(t-amylperoxy)butyl
N-[1-{3(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,
1,3-dimethyl-3-(cumylperoxy))butyl
N-[1-{3-(1-methylethenyl)-phenyl}-1-methylethyl]carbamate,
1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane,
1,1-di(t-butylperoxy)cyclohexane, n-butyl
4,4-di(t-amylperoxy)valerate, ethyl 3,3-di(t-butylperoxy)butyrate,
2,2-di(t-amylperoxy)propane,
3,6,6,9,9-pentamethyl-3-ethoxycabonylmethyl-1,2,4,5-tetraoxacyclononane,
n-buty 1-4,4OO-t-amyl-O-hydrogen-monoperoxy-succinate, 3,6,9,
triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane (or methyl ethyl
ketone peroxide cyclic trimer), methyl ethyl ketone peroxide cyclic
dimer, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane,
2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl perbenzoate,
t-butylperoxy acetate, t-butylperoxy-2-ethyl hexanoate, t-amyl
perbenzoate, t-amyl peroxy acetate, t-butyl peroxy isobutyrate,
3-hydroxy-1,1-dimethyl t-butyl peroxy-2-ethyl hexanoate,
OO-t-amyl-O-hydrogen-monoperoxy succinate,
OO-t-butyl-O-hydrogen-monoperoxy succinate, di-t-butyl
diperoxyphthalate, t-butylperoxy (3,3,5-trimethylhexanoate),
1,4-bis(t-butylperoxycarbo)cyclohexane,
t-butylperoxy-3,5,5-trimethylhexanoate,
t-butyl-peroxy-(cis-3-carboxy)propionate, allyl
3-methyl-3-t-butylperoxy butyrate, OO-t-butyl-O-isopropylmonoperoxy
carbonate, OO-t-butyl-O-(2-ethyl hexyl) monoperoxy carbonate,
1,1,1-tris[2-(t-butylperoxy-carbonyloxy)ethoxymethyl]propane,
1,1,1-tris[2-(t-amylperoxy-carbonyloxy)ethoxymethyl]propane,
1,1,1-tris[2-(cumylperoxy-cabonyloxy)ethoxymethyl]propane,
OO-t-amyl-O-isopropylmonoperoxy carbonate,
di(4-methylbenzoyl)peroxide, di(3-methylbenzoyl)peroxide,
di(2-methylbenzoyl)peroxide, didecanoyl peroxide, dilauroyl
peroxide, 2,4-dibromo-benzoyl peroxide, succinic acid peroxide,
dibenzoyl peroxide, di(2,4-dichloro-benzoyl)peroxide, and
combinations thereof.
In one or more embodiments, radical initiators may include
azo-compounds such as azobisisobutyronitrile (AIBN),
2,2'-azobis(amidinopropyl) dihydrochloride, and the like,
azo-peroxide initiators that contain mixtures of peroxide with
azodinitrile compounds such as
2,2'-azobis(2-methyl-pentanenitrile),
2,2'-azobis(2methyl-butanenitrile),
2,2'-azobis(2-ethyl-pentanenitrile),
2-[(1-cyano-1-methylpropyl)azo]-2-methyl-pentanenitrile,
2-[(1-cyano-1-ethylpropyl)azo]-2-methyl-butanenitrile,
2-[(1-cyano-1-methylpropyl)azo]-2-ethyl, and the like.
In one or more embodiments, radical initiators may include
Carbon-Carbon ("C--C") free radical initiators such as
2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane,
3,4-diethyl-3,4-diphenylhexane, 3,4-dibenzyl-3,4ditolylhexane,
2,7-dimethyl-4,5-diethyl-4,5-diphenyloctane,
3,4-dibenzyl-3,4-diphenylhexane, and the like.
In one or more embodiments, polymer compositions in accordance with
the present disclosure may be formed from one or more radical
initiators present at a percent by weight of the total
polymerization mixture (wt %) that ranges from a lower limit
selected from one of 0.000001 wt %, 0.0001 wt %, 0.01 wt %, 0.1 wt
%, 0.15 wt %, 0.4 wt %, 0.6 wt %, 0.75 wt % and 1 wt %, to an upper
limit selected from one of 0.5 wt %, 1.25 wt %, 2 wt %, 4 wt %, and
5 wt %, where any lower limit can be used with any upper limit.
Further, it is envisioned that the concentration of the radical
initiator may be more or less depending on the application of the
final material.
Stabilizers
Polymer compositions in accordance with the present disclosure may
include one or more stabilizers capable of preventing
polymerization in the feed lines of monomers and comonomers but not
hindering polymerization at the reactor.
In one or more embodiments, stabilizers may include nitroxyl
derivatives such as 2,2,6,6-tetramethyl-1-piperidinyloxy,
2,2,6,6-tetramethyl-4-hydroxy-1-piperidinyloxy,
4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy,
2,2,6,6-tetramethyl-4-amino-piperidinyloxy, and the like.
In one or more embodiments, polymer compositions in accordance with
the present disclosure be formed from one or more stabilizers
present at a percent by weight of the total polymerization mixture
(wt %) of one or more stabilizers that ranges from a lower limit
selected from one of 0.000001 wt %, 0.0001 wt %, 0.01 wt %, 0.1 wt
%, 0.15 wt %, 0.4 wt %, 0.6 wt %, 0.75 wt % and 1 wt %, to an upper
limit selected from one of 0.5 wt %, 1.25 wt %, 2 wt %, 4 wt %, and
5 wt %, where any lower limit can be used with any upper limit.
Further, it is envisioned that the concentration of the stabilizer
may be more or less depending on the application of the final
material.
Additives
Polymer compositions in accordance with the present disclosure may
include fillers and additives that modify various physical and
chemical properties when added to the polymer composition during
blending that include one or more polymer additives such as
kickers, processing aids, lubricants, antistatic agents, clarifying
agents, nucleating agents, beta-nucleating agents, slipping agents,
antioxidants, antacids, light stabilizers such as HALS, IR
absorbers, whitening agents, organic and/or inorganic dyes,
anti-blocking agents, processing aids, flame-retardants,
plasticizers, biocides, and adhesion-promoting agents.
Polymer compositions in accordance with the present disclosure may
include one or more inorganic fillers such as talc, glass fibers,
marble dust, cement dust, clay, carbon black, feldspar, silica or
glass, fumed silica, silicates, calcium silicate, silicic acid
powder, glass microspheres, mica, metal oxide particles and
nanoparticles such as magnesium oxide, antimony oxide, zinc oxide,
inorganic salt particles and nanoparticles such as barium sulfate,
wollastonite, alumina, aluminum silicate, titanium oxides, calcium
carbonate, polyhedral oligomeric silsesquioxane (POSS).
In one or more embodiments, polymer compositions in accordance with
the present disclosure may contain a percent by weight of the total
composition (wt %) of one or more additives and/or fillers that
ranges from a lower limit selected from one of 0.01wt %, 0.02 wt %,
0.05 wt %, 1.0 wt %, 5.0 wt %, 10.0 wt %, 15.0 wt %, and 20.0 wt %,
to an upper limit selected from one of 25 wt %, 30 wt %, 40 wt %,
50 wt %, 60 wt %, and 70 wt %, where any lower limit can be used
with any upper limit.
Polymer Composition Preparation Methods
In one or more embodiments, polymer compositions in accordance with
the present disclosure may be prepared in reactor by polymerizing
ethylene and one or more vinyl carbonyl and/or diene monomers.
Methods of reacting the comonomers in the presence of a radical
initiator may include any suitable method in the art including
solution phase polymerization, pressurized radical polymerization,
bulk polymerization, emulsion polymerization, and suspension
polymerization. In some embodiments, the reactor may be a batch or
continuous reactor at pressures below 500 bar, known as low
pressure polymerization system. In particular embodiments, the
reactor pressure may be above 40 bar, and the reactor temperature
may be above 50.degree. C., and including the conditions known as
high pressure polymerizations. In one or more embodiments, the
reaction is carried out in a low pressure polymerization process
wherein the ethylene and one or more vinyl carbonyl are polymerized
in a liquid phase of an inert solvent and/or one or more liquid
monomer(s). In one embodiment, polymerization comprises initiators
for free-radical polymerization in an amount from about 0.0001 to
about 0.01 milimoles calculated as the total amount of one or more
initiator for free-radical polymerization per liter of the volume
of the polymerization zone. The amount of ethylene in the
polymerization zone will depend mainly on the total pressure of the
reactor in a range from about 20 bar to about 500 bar and
temperature in a range from about 20.degree. C. to about
200.degree. C. In one or more embodiments, the pressure in the
reactor may have a lower limit of any of 20, 30, 40, 50, 75, or 100
bar, and an upper limit of any of 100, 150, 200, 250, 300, 350,
400, 450 or 500 bar. The liquid phase of the polymerization process
in accordance with the present disclosure may include ethylene, one
or more vinyl carbonyl monomer, initiator for free-radical
polymerization, and optionally one or more inert solvent such as
tetrahydrofuran (THF), chloroform, dichloromethane (DCM), dimethyl
sulfoxide (DMSO), dimethyl carbonate (DMC), hexane, cyclohexane,
ethyl acetate (EtOAc) acetonitrile, toluene, xylene, ether,
dioxane, dimethyl-formamide (DMF), benzene or acetone. Copolymers
and terpolymers produced under low-pressure conditions may exhibit
number average molecular weights of 1 to 300 kDa, weight average
molecular weights of 1 to 1000 kDa and MWDs of 1 to 60.
In some embodiments, the comonomers and one or more free-radical
polymerization initiators are polymerized in a continuous or batch
process at temperatures above 70 .degree. C. and at pressures above
1000 bar, known as high pressure polymerization systems. For
example, a pressure of greater than 1000, 1100, 1200, 1500, 1600,
1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 3000, 5000,
or 10000 bar may be used. Copolymers and terpolymers produced under
high-pressure conditions may have number average molecular weights
(M.sub.n) of 1 to 10000 kDa, weight average molecular weights
(M.sub.w) of 1 to 20000 kDa. Molecular weight distribution (MWD) is
obtained from the ratio between the weight average molecular weight
(M.sub.w) and the number average molecular weight (M.sub.n)
obtained by GPC. Copolymers and terpolymers produced under
high-pressure conditions may have MWDs of 1 to 60.
In some embodiments, the conversion during polymerization in low
pressure polymerization and high pressure polymerization systems,
which is defined as the weight or mass flow of the produced polymer
divided by the weight of mass flow of monomers and comonomers may
have a lower limit of any of 0.01%, 0.1%, 1%, 2%, 5%, 7%, 10% and a
upper limit of any of 15%, 17%, 20%, 25%, 30%, 35%, 40%, 45%, 50%,
60%, 70%, 80%, 90%, 99% or 100%.
Physical Properties
In one or more embodiments, polymer compositions may have a melt
flow rate (MFR) according to ASTM D1238 at 190.degree. C./2.16 kg
in a range having a lower limit selected from any of 0.01 g/10 min,
0.5 g/10 min, 1 g/10 min, and 10 g/10 min, to an upper limit
selected from any of 50 g/10min, 350 g/10 min, 450 g/10 min, 550
g/10 min, 1000 g/10 min, and 2000 g/10 min, where any lower limit
may be paired with any upper limit.
In one or more embodiments, polymer compositions may have
crystallinity measured according to ASTM D3418 by differential
scanning calorimetry (DSC) or wide angle X-ray diffraction (WAXD)
in a range having a lower limit selected from any 0.1%, 1%, 10%,
and 20%, to an upper limit selected from any of 60%, 70%, and 80%,
where any lower limit may be paired with any upper limit.
In one or more embodiments, polymer compositions may have a glass
transition temperature (T.sub.g) measured by dynamic mechanical
analysis (DMA) or DSC in a range having an upper limit selected
from any 100.degree. C., 90.degree. C., and 80.degree. C., to a
lower limit selected from any of -50.degree. C., -60.degree. C.,
and -70.degree. C., where any lower limit may be paired with any
upper limit.
In one or more embodiments, polymer compositions may have a melting
temperature (T.sub.m) measured according to ASTM D3418 by DSC in a
range having a lower limit selected from any 20.degree. C.,
30.degree. C., and 40.degree. C., to an upper limit selected from
any of 100.degree. C., 110.degree. C., 120.degree. C., 130.degree.
C., 140.degree. C., and 150.degree. C., where any lower limit may
be paired with any upper limit. In some embodiments, polymer
compositions may not present a Tm, characterizing a completely
amorphous polymer composition.
In one or more embodiments, polymer compositions may have a
crystallization temperature (T.sub.c) measured according to ASTM
D3418 by DSC in a range having a lower limit selected from any 0,
5.degree. C., 10.degree. C., 20.degree. C., and 30.degree. C., and
to an upper limit selected from any of 80.degree. C., 90.degree.
C., 100.degree. C., 110.degree. C., 120.degree. C., 130.degree. C.,
140.degree. C., and 150.degree. C., where any lower limit may be
paired with any upper limit.
In one or more embodiments, polymer compositions may have a heat of
crystallization measured according to ASTM D3418 by DSC in a range
having a lower limit of any of 0, 10, 20, 30, 40, 50, and 60 J/g,
and an upper limit of any of 140, 180, 200, 240, and 280 J/g, where
any lower limit may be paired with any upper limit.
The polymerization conditions result in the production of polymers
having a wide range of molecular weight distribution (MWD). In one
of the embodiment, the MWD of a polymer obtained within this
polymerization method is from about 1 to about 60, with a lower
limit of any of 1, 1.5, 3, 5, or 10, and an upper limit of any of
10, 20, 30, 40, 50 or 60, where any lower limit can be used in
combination with any upper limit. However, depending on the amount
of comonomer incorporated, samples produced under high-presure
conditions show a broad range of MWDs from about 1 to 60.
Copolymers and terpolymers produced under low-pressure conditions
may exhibit number average molecular weights of 1 to 300 kDa,
weight average molecular weights of 1 to 1000 kDa and MWDs of 1 to
60. On the other hand, copolymers and terpolymers produced under
high-pressure conditions may show number average molecular weights
of 1 to 10000 kDa, weight average molecular weights of 1 to 20000
kDa and MWDs of 1 to 60.
In one or more embodiments, polymer compositions may have a
hardness of the polymer composition as determined according to ASTM
D2240 in a range having a lower limit selected from any 25, 35, and
45 Shore A, to an upper limit selected from any of 80, 90, and 100
Shore A, where any lower limit may be paired with any upper
limit.
In one or more embodiments, polymer compositions may have a
hardness of the polymer composition as determined according to ASTM
D2240 in a range having a lower limit selected from any 10, 20, and
30 Shore D, to an upper limit selected from any of 50, 60, and 70
Shore D, where any lower limit may be paired with any upper
limit.
In one or more embodiments, polymer compositions may have a percent
elongation, tensile strength, and modulus as determined according
to ASTM D368 in a range having a lower limit selected from any 10,
50, and 100 percent elongation, to an upper limit selected from any
of 500, 1000, and 2000 percent elongation, a lower limit selected
from any 1, 5, and 10 MPa tensile strength, to an upper limit
selected from any of 15, 30, 70, 100, 200, and 500 MPa tensile
strength, a lower limit selected from any 0.1, 1, 5, 20, and 40 MPa
modulus, to an upper limit selected from any of 100, 200, 300, 500,
1000, 2000, 5000, and 10000 MPa modulus, and where any lower limit
may be paired with any upper limit.
In one or more embodiments, polymer compositions may have a density
according to ASTM D792 in a range having a lower limit selected
from any of 0.75 g/cm.sup.3, 0.85 g/cm.sup.3, and 0.89 g/cm.sup.3,
to an upper limit selected from any of 1.1 g/cm.sup.3, 1.2
g/cm.sup.3, and 1.3 g/cm.sup.3, where any lower limit may be paired
with any upper limit.
In one or more embodiments, polymer compositions may have a
bio-based carbon content, as determined by ASTM D6866-18 Method B,
in a range having a lower limit selected from any of 1%, 5%, 10%,
and 20%, to an upper limit selected from any of 60%, 80%, 90%, and
100%, where any lower limit may be paired with any upper limit.
In one or more embodiments, polymers may have a long chain
branching frequency ranging from 0 to 10, such as from a lower
limit of any of 1, 0.5, 1, or 1.5 and an upper limit of any of 2,
4, 6, 8, or 10, where any lower limit may be paired with any upper
limit.
In one or more embodiments, long chain branching average LCBf may
be calculated from GPC analysis using a GPC instrument equipped
with IR5 infrared detector and a four-capillary viscometry
detector, both from Polymer Char. Data collection was performed
using Polymer Char's software. The concentration measured by IR5
detector was calculated considering that the whole area of the
chromatogram was equivalent to the elution of 100% of the mass
injected. Average LCBf was then calculared according to:
.times..times..times..times..times..times. ##EQU00001## where R is
the molar mass of the repeated unit and is calculated based on the
contribution of monomer and comonomers, considering the mol
percentage of each one, determined by NMR. M.sub.w is the weight
average molecular weight and is calculated according to the
following equation by means of universal calibration:
.SIGMA..function..times..SIGMA..function..times. ##EQU00002##
Average B.sub.n constant is calculated according to:
.times..times..pi. ##EQU00003## Average g' and g constants are
calculated according to:
'.times..times..times..times..times..times..times..times..times..times..-
times..times. ##EQU00004## ' ##EQU00004.2## .epsilon. is known as
the viscosity shielding ratio and is assumed to be constant and
equal to 0.7.
The intrinsic viscosity of the branched samples (IV.sub.branched)
may be calculated using the specific viscosity (.eta..sub.sp) from
the viscometer detector as follows.
.times..tau..times..times..times..times..times..times..SIGMA..function..e-
ta..times..times..DELTA..times..times..times..times. ##EQU00005##
where SA is sample amount, KIV is viscosity detector constant and
the volume increment (.DELTA.V) is a constant determined by the
difference between consecutive retention volumes
(.DELTA.V=RV.sub.i+1-RV.sub.i).
The intrinsic viscosity of the linear counterpart (IV.sub.linear)
may be calculated using Mark-Houwink equation, whereas the
Mark-Houwink constants are obtained from the intrinsic viscosity
considering the concentration from Stacy-Haney method as follows.
The Stacey-Haney IV (IV.sub.SH) is calculated based on Stacy-Haney
concentration by
.times..times..eta. ##EQU00006## where C.sub.SH is found from
.times..times..times..eta..times..times. ##EQU00007## whereas
.eta..sub.rel is the relative viscosity
(.eta..sub.rel=.eta..sub.sp+1), (hv).sub.i is the hydrodynamic
volume at each elution volume slice from the universal calibration
curve and the Mark-Houwink exponent, a, was defined as 0.725,
reference value for a linear polyethylene homopolymer and the
constant, K, is calculated according to:
.times..DELTA..times..SIGMA..function..times..times..eta..times.
##EQU00008## From IV.sub.SH.sub.i the molecular weight (M.sub.SH)
on each elution volume slice is also obtained according to
.times..times. ##EQU00009##
Plotting IV.sub.SH.sub.i versus M.sub.SH.sub.i, both in log scale,
leads to Mark-Houwink constants k and a for the linear polymer.
Finally, IV.sub.iinear may be calculated as:
IV.sub.linear=kM.sub.v.sup.a where M.sub.v is the viscosity average
molecular weight by means of universal calibration and the
concentration by IR5 infrared detector, and is calculated according
to:
.SIGMA..function..times..SIGMA..function..times..times.
##EQU00010## where N.sub.i is the number of ith molecules with
molecular weight of M.sub.i. The M.sub.i is obtained considering
the concentration by IR5 infrared detector and the hydrodynamic
volume from the universal calibration
.times..times..eta. ##EQU00011## M.sub.i is plotted against the
retention volume, the noisy extremes of the curve are removed and
then extrapolated using a third order fit polynomial. The equation
derived from this 3.degree. order fit polynomial is used to
calculate the M.sub.i as a function of retention volume. In one or
more embodiments, polymers may have a long chain branching
frequency, calculated by GPC analysis, ranging from 0 to 10, such
as from a lower limit of any of 1, 0.5, 1, or 1.5 and an upper
limit of any of 2, 4, 6, 8, or 10, where any lower limit may be
paired with any upper limit.
In one or more embodiments, polymers may have a long chain
branching content, measured by .sup.13CNMR, ranging from 0 to 10,
such as a lower limit of any of 0, 0.2, 0.4, 0.6, 0.8, or 1 and an
upper limit of any of 2, 4, 6, 8, or 10, where any lower limit may
be paired with any upper limit.
In .sup.13CNMR analysis, long chain branching (LCB) is defined as
any branch with six or more carbons. Based on .sup.13CNMR spectra,
LCB content (B.sub.6+) in branched polymers is calculated from:
B.sub.6+=S.sub.3, Polymer-S.sub.3, vinyl carbonyl monomers where
the S.sub.3 peak is positioned at 32.2 ppm on a .sup.13CNMR
spectrum. This method takes into account both branches (B.sub.6+)
and the chain ends of the main chain, where the effect of the long
branches in the vinyl carbonyl monomer is corrected using its
.sup.13CNMR spectrum, and the effect of chain ends can also be
corrected with GPC data.
In one or more embodiments, the polymers may have, after thermal
fractionation by successive self-nucleation and annealing (SSA), a
heat flow versus temperature curve that has 0 to 20 minimums, such
as a lower limit of any of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10
minimums and an upper limit of any of 12, 14, 16, 18, or 20
minimums, where any lower limit may be paired with any upper limit,
where the minimums may be allocated in the temperature ranges of
140-150.degree. C., 130-140.degree. C., 120-130.degree. C.,
110-120.degree. C., 100-110.degree. C., 90-100.degree. C.,
80-90.degree. C., 70-80.degree. C., 60-70.degree. C., 50-60.degree.
C., 40-50.degree. C., 30-40.degree. C., 20-30.degree. C.,
10-20.degree. C., and/or 0-10.degree. C. Such thermal fractionation
may use a temperature protocol (a series of heating and cooling
cycles) to produce a distribution of lamellar crystals whose sizes
reflect the distribution of methyl sequence lengths in the
copolymers and terpolymers. The thermal fractionation may be
carried out in a TA Instruments Discovery DSC 2500, under nitrogen.
All cooling cycles may be carried out at 5.degree. C./min, and
heating cycles may be carried out at 20.degree. C./min. Samples may
be heated from 25.degree. C. to 150.degree. C., held at 150.degree.
C. for 5 min, cooled to 25.degree. C. and held at this temperature
for 3 min. The sample may subsequently be heated to the first
annealing temperature (140.degree. C.), held at this temperature
for 5 min and cooled to 25.degree. C. The sample may then be heated
again to the next annealing temperature (130.degree. C.), held at
this temperature for 5 min and cooled to 25.degree. C. The
procedure may be repeated in steps of 10.degree. C. until the last
annealing temperature (such as, but not limited to, 0.degree. C.)
is reached. Then, the sample may be heated to 150.degree. C., at
20.degree. C./min in order to obtain the melting profile.
In one or more embodiments, polymers may have a thermal stability,
measured by thermal gravimetric analysis (TGA), where the ratio of
weight loss between 250 to 400.degree. C. relative to the total
comonomer content ranges from 0 to 2, such as a lower limit of any
of 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1, and an
upper limit of any of 1.2, 1.4, 1.6, 1.8, or 2, where any lower
limit may be paired with any upper limit.
In one or more embodiments, polymers may have a storage modulus at
0.degree. C. of 1 to 50 GPa, such as a lower limit of any of 1, 2,
5, 10, 20, 40, 60, 80, or 100 MPa, and an upper limit of any of 200
MPa, 300 MPa, 400 MPa, 500 MPa, 700 MPa, 1 GPa, 5 GPa, 10 GPa, 20
GPa, 30 GPa, 40 GPa, or 50 GPa where any lower limit may be paired
with any upper limit.
In one or more embodiments, polymers may have one to two relaxation
maximums in the tan .delta. versus temperature plot between -75 to
75.degree. C. where the peak at the higher temperature is
designated as .alpha. and the peak at lower temperature is
designated as .beta.. In one or more embodiments, T.sub..alpha.
(temperature corresponding to the .alpha. peak) can vary between
-75 to 75.degree. C., such as a lower limit of any of -75, -60,
-50, -40, -30, -20, -10, or 0.degree. C., and an upper limit of any
of 10, 20, 30, 40, 50, 60, or 75.degree. C., where any lower may be
paired with any upper limit. In one or more embodiments,
T.sub..beta. (temperature corresponding to the .beta. peak) can
vary between -75 to 50.degree. C., such as a lower limit of any of
-75, -60, -50, -40, -30, -20, -10, or 0.degree. C., and an upper
limit of any of 10, 20, 30, 40, or 50.degree. C., where any lower
may be paired with any upper limit.
APPLICATIONS
In one or more embodiments, polymer compositions can be used in
various molding processes, including extrusion molding, injection
molding, thermoforming, cast film extrusion, blown film extrusion,
foaming, extrusion blow-molding, ISBM (Injection Stretched
Blow-Molding), 3D printing, rotomolding, pultrusion, and the like,
to produce manufactured articles.
Polymer compositions in accordance with the present disclosure may
also be formulated for a number of polymer articles, including the
production of seals, hoses, footwear insoles, footwear midsoles,
footwear outsoles, automotive parts and bumpers, sealing systems,
hot melt adhesives, films, conveyor belts, sportive articles,
rotomolded articles, primers, in civil construction as linings,
industrial floors, acoustic insulation, and the like.
In one or more embodiments, polymer compositions may be included in
polymer blends with one or more polymer resins. In some
embodiments, polymer compositions may be formulated as a
masterbatch that is added at a percent by weight of 1 wt % to 99 wt
% to a polymer resin.
The following examples are merely illustrative, and should not be
interpreted as limiting the scope of the present disclosure.
EXAMPLE 1
Ethylene vinyl acetate (EVA) copolymers account for a large portion
of the ethylene copolymer market and have a range of properties
dependent on the vinyl acetate content. An increase in vinyl
acetate incorporation results in a decrease in crystallinity, glass
transition temperature, melting temperature, and chemical
resistance while increasing optical clarity, impact and stress
crack resistance, flexibility and adhesion. In this example,
ethylene-based polymers incorporating various amounts of vinyl
acetate and a vinyl carbonyl monomer VeoVa.TM. 10 from HEXION.TM.
(a mixture of isomers of vinyl esters of versatic acid having a
carbon number of 10) were produced to assay a number of polymer
properties for the resulting compositions.
Ethylene (99.95%, Air Liquide, 1200 psi), VeoVa.TM. 10 (Hexion) and
2,2'-azobisisobutyronitrile (AIBN, 98% Sigma Aldrich) were used as
received. Dimethyl carbonate (DMC, anhydrous 99%, Sigma Aldrich),
and vinyl acetate (99%, Sigma Aldrich) were distilled before use
and stored under nitrogen.
Synthesis of terpolymers with ethylene, vinyl acetate and VeoVa.TM.
10 (Samples A1-A5)
Polymer compositions were prepared using a free radical
polymerization of the comonomer mixtures in solution by combining
80 g of dimethyl carbonate (DMC), 9.97 or 14.98 g of vinyl acetate,
13.5 or 11.48 g VeoVa.TM. 10, and 0.1 g of azobisisobutyronitrile
(AIBN) to a Parr reactor. The reactor was sealed and flushed 3
times with ethylene with 1000 psi of pressure while stirring. The
system was then heated at 70.degree. C. at an ethylene pressure of
1200 psi and stirred for 2 hours. The reaction mixture was
collected and the reactor was washed with THF at 60.degree. C. The
solvent in the reaction mixture and wash was removed by rotary
evaporation. The resulting polymer was dissolved in THF and
precipitated into cold methanol, then vacuum filtered.
EXAMPLE 2
Ethylene-based polymers incorporating various amounts of vinyl
pivalate, vinyl laurate and vinyl 4-tert-butylbenzoate were
produced to assay a number of polymer properties for the resulting
compositions.
Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile
(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate
(DMC, anhydrous 99%, Sigma Aldrich), vinyl acetate (99%, Sigma
Aldrich), vinyl pivalate (99%, Sigma Aldrich), vinyl laurate (99%,
Sigma Aldrich) and vinyl 4-tert-butylbenzoate (99%, Sigma Aldrich)
were distilled before use and stored under nitrogen.
Synthesis of terpolymers with ethylene, vinyl acetate and vinyl
pivalate, vinyl laurate and vinyl 4-tert-butylbenzoate (Samples
B1-B3)
Polymer compositions were prepared using a free radical
polymerization of the comonomer mixtures in solution by combining
80 g of dimethyl carbonate (DMC), 9.3 g of vinyl acetate and 13.9 g
of vinyl pivalate or 24.4 g of vinyl laurate or 22 g vinyl
4-tert-butylbenzoate, and 0.1 g of azobisisobutyronitrile (AIBN) to
a Parr reactor. The reactor was sealed and flushed 3 times with
ethylene with 1000 psi of pressure while stirring. The system was
then heated at 70.degree. C. at an ethylene pressure of 1200 psi
and stirred for 2 hours. The reaction mixture was collected and the
reactor was washed with THF at 60.degree. C. The solvent in the
reaction mixture and wash was removed by rotary evaporation. The
resulting polymer was dissolved in THF and precipitated into cold
methanol, then vacuum filtered.
EXAMPLE 3
Ethylene-based polymers incorporating various amounts of vinyl
acetate and a vinyl carbonyl monomer VeoVa.TM. 10 from HEXION.TM.,
a mixture of isomers of vinyl esters of versatic acid having a
carbon number of 10 under high-pressure conditions were produced to
assay a number of polymer properties for the resulting
compositions.
Ethylene, VeoVa.TM. 10 (Hexion), tertbutylperoxy-2-ethylhexanoate,
heptane (99%, Sigma Aldrich), and vinyl acetate (99%, Sigma
Aldrich) were used as received.
Synthesis of terpolymers with ethylene, vinyl acetate and VeoVa.TM.
10 were performed under high-pressure conditions (Samples
D1-D15).
Polymer compositions were prepared using a continuous free radical
polymerization.TM. 10, heptane and tertbutylperoxy-2-ethylhexanoate
into a high-pressure reactor. Before each round of polymerization,
the reactor was purged five times with 2200-2300 bars of ethylene.
Each reaction began by heating the reactor to 200.degree. C. and
feeding ethylene to a pressure of 1900-2000 bar. A continuous flow
of ethylene with a rate of 2000 g/hr was then fed into the reactor.
Once the targeted pressure and stable ethylene flow was achieved,
the comonomers were added to the reactor. The mixture of initiator
and heptane was introduced to the system at a flow rate of 2 mL/hr.
The reaction mixtures was collected and the reactor was washed with
xylene at 145.degree. C. The resulting polymer was dissolved in
xylene and precipitated into cold methanol, then vacuum
filtered.
EXAMPLE 4
In this example, an ethylene-based polymer was produced by
incorporating trimethylsilyl-protected methyl vinyl glycolate to
assay a number of polymer properties for the resulting
compositions.
Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile
(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate
(DMC, anhydrous 99%, Sigma Aldrich) was distilled before use and
stored under nitrogen.
Synthesis of copolymer with ethylene and trimethylsilyl-protected
methyl vinyl glycolate (Sample E1)
8 g trimethylsilyl-protected methyl vinyl glycolate, 80 g dimethyl
carbonate and 0.1 g of azobisisobutyronitrile were added to a 300
mL Parr reactor. The reactor was sealed and flushed three times
with 1000 psi pressure of nitrogen while stirring. The system was
then heated, at 70.degree. C. at an ethylene pressure of 1200 psi
and allowed to stir for the desired time. The reaction mixture was
collected and the reactor was washed with THF at 60.degree. C. The
solvent in the reaction mixture and wash was removed by rotary
evaporation. The resulting polymer was dissolved in THF and
precipitated into cold methanol, then vacuum filtered.
EXAMPLE 5
In this example, an ethylene-based polymer was produced by
incorporating vinyl acetate and trimethylsilyl-protected methyl
vinyl glycolate to assay a number of polymer properties for the
resulting compositions.
Ethylene (99.95%, Air Liquide, 1200 psi) and azobisisobutyronitrile
(AIBN, 98% Sigma Aldrich) were used as received. Dimethyl carbonate
(DMC, anhydrous 99%, Sigma Aldrich) and vinyl acetate (99%, Sigma
Aldrich) were distilled before use and stored under nitrogen.
Synthesis of terpolymer with ethylene, vinyl acetate and
trimethylsilyl-protected methyl vinyl glycolate (Sample E2)
5 g trimethylsilyl-protected methyl vinyl glycolate, 15 g vinyl
acetate, 80 g dimethyl carbonate and 0.1 g of
azobisisobutyronitrile were added to a 300 mL Parr reactor. The
reactor was sealed and flushed three times with 1000 psi pressure
of nitrogen while stirring. The system was then heated, at
70.degree. C. at an ethylene pressure of 1200 psi and allowed to
stir for the desired time. The reaction mixture was collected and
the reactor was washed with THF at 60.degree. C. The solvent in the
reaction mixture and wash was removed by rotary evaporation. The
resulting polymer was dissolved in THF and precipitated into cold
methanol, then vacuum filtered.
EXAMPLE 6
In this example, ethylene-based polymers incorporating by
incorporating methyl vinyl glycolate under high pressure conditions
were produced to assay a number of polymer properties for the
resulting compositions.
Ethylene and tertbutylperoxy-2-ethylhexanoate were used as
received. Toluene (99%, Sigma Aldrich) was distilled before use and
stored under nitrogen.
Synthesis of copolymers with ethylene and methyl vinyl glycolate
under high pressure conditions (Samples E3-E4)
Polymer compositions were prepared using a batch free radical
polymerization of the comonomer mixture by combining 0.45 g methyl
vinyl glycolate, toluene and various amounts of
tertbutylperoxy-2-ethylhexanoate into a high-pressure reactor.
Before each round of polymerization, the reactor was purged five
times with 2200-2300 bars of ethylene. Each reaction began by
heating the reactor to 200.degree. C. and feeding ethylene to a
pressure of 1900-2000 bar. Once the targeted pressure and stable
ethylene flow was achieved, the comonomers were added to the
reactor. The mixture of initiator and toluene was then introduced
to the system. The reaction mixtures were collected, and the
reactor was washed with xylene at 145.degree. C. The resulting
polymer was dissolved in xylene and precipitated into cold
methanol, then vacuum filtered.
Polymer Characterization
Twenty-seven samples of ethylene-based polymers denoted A1-A5,
B1-B3, D1-D15 and E1-E4 were purified and characterized. The
ethylene-based polymers contained varying amounts of both vinyl
acetate and a vinyl carbonyl monomer.
TABLE-US-00001 TABLE 1 Reaction Summary with NMR and GPC Results
for Examples 1 to 6 Vinyl 4- Methyl Trimethylsilyl- Vinyl VeoVa
.TM. Vinyl Vinyl tert-butyl Vinyl Protected Methyl Acetate 10
Pivalate Laurate bezoate Glycolate Vinyl Glycolate M.sub.w M.sub.n
Conversion Samples (wt %).sup.a,b (wt %).sup.a,b (wt %).sup.a,b (wt
%).sup.a,b (wt %).sup.a,b (w %).sup.a,b (w %).sup.a,b (kDa) (kDa)
MWD (%) A1 11.4 23.4 -- -- -- -- -- 27.0 13.0 2.1 -- A2 10.2 18.7
-- -- -- -- -- 25.9 11.3 2.3 -- A3 9.1 22.2 -- -- -- -- -- 20.3
10.1 2.0 -- A4 14.4 26.1 -- -- -- -- -- 18.7 8.3 2.3 -- A5 14.7
22.6 -- -- -- -- -- 22.6 10.3 2.2 -- B1 11.2 -- 16.7 -- -- -- --
23.4 8.1 2.9 -- B2 9.5 -- -- 27.7 -- -- -- 22.3 5.1 4.4 -- B3 16.0
-- -- -- 47.4 -- -- 11.9 4.2 2.8 -- D1 -- 3.3 -- -- -- -- -- 1173.3
67.7 17.3 17.5 D2 -- 4.6 -- -- -- -- -- 996.7 61.1 16.3 14.5 D3 --
8.3 -- -- -- -- -- 537.6 48.9 11.0 15.8 D4 -- 10.8 -- -- -- -- --
425.1 41.9 10.1 8.2 D5 -- 19.2 -- -- -- -- -- 220.6 22.7 9.7 6.7 D6
-- 25.5 -- -- -- -- -- 207.2 24.3 8.5 4.8 D7 4.8 23.9 -- -- -- --
-- 64.2 19.0 3.4 4.2 D8 10.2 19.7 -- -- -- -- -- 55.5 16.9 3.3 5.9
D9 15.7 14.2 -- -- -- -- -- 57.6 20.2 2.9 15.6 D10 20.5 9.9 -- --
-- -- -- 55.1 17.3 3.2 16.4 D11 25.0 1.9 -- -- -- -- -- 75.3 19.8
3.8 14.2 D12 29.1 -- -- -- -- -- -- 52.8 15.3 3.4 16.9 D13 -- 22.4
-- -- -- -- -- 52.1 10.7 4.9 5 D14 21.2 8.4 -- -- -- -- -- 48.6
11.6 4.2 6 D15 25.8 5.0 -- -- -- -- -- 56.5 10.5 5.4 12.2 E1 -- --
-- -- -- -- 10.3 2.8 1.0 2.8 -- E2 30.1 -- -- -- -- -- 1.1 3.6 1.3
2.8 -- E3 -- -- -- -- -- 0.89 -- 184.7 6.1 30.5 -- E4 -- -- -- --
-- 5.01 -- 97.3 3.9 25.1 -- M1 28.sup.a -- -- -- -- -- -- 78.5 13.5
5.8 -- M2 28.sup.a -- -- -- -- -- -- 59.3 14.5 4.1 --
.sup.aDetermined from .sup.1H NMR; .sup.bDetermined from .sup.13C
NMR; MW and MWD are found using a GPC equipped with a viscometer
detector. Conversion is calculated using mass flow of monomers and
produced polymer.
Table 1 provides a summary of the gel permeation chromatography
(GPC) and nuclear magnetic resonance (NMR) data for all polymers
synthesized and two comparative commercial EVA samples M1-M2.
For the polymer samples containing the vinyl carbonyl monomers,
incorporation was determined using quantitative .sup.13C NMR, since
the .sup.1H NMR contained significant overlap in both the carbonyl
and alkyl regions for accurate integration. The carbonyl peaks not
observed in pure EVA .sup.13C NMR were identified as coming from
the branched vinyl carbonyl monomer units and used to calculate the
weight percent of the comonomer.
With particular respect to FIG. 1, the full .sup.13C NMR spectra
(TCE-D.sub.2, 393.1 K, 125 MHz) for the VeoVa.TM. acid 10 monomer
and representative samples A2 and M1 are shown. There is evidence
of incorporation of the branched vinyl ester seen in both the
carbonyl (170-180 ppm) and alkyl regions (0-50 ppm). The spectra
show a significant increase in the peaks indicative of carbonyl
carbons and long alkyl chains within the branched vinyl ester.
General peak assignments are also shown in FIG. 1. When comparing
spectra of the VeoVa.TM. acid 10 monomer and the polymer A2, the
polymer spectrum exhibits a disappearance of the vinyl peaks and
appearance of peaks corresponding to all three comonomers studied
(ethylene, vinyl acetate, and VeoVa.TM. acid 10). The abundant
number of peaks in both regions may be due to the mixture of
isomers in the VeoVa.TM. acid 10 monomer, and the appearance of
these peaks in the polymer samples validates the formation of the
respective terpolymer.
Further evidence of the incorporation of the VeoVa.TM. acid 10
monomer is demonstrated in FIG. 2 showing the .sup.1H NMR spectra
(TCE-D.sub.2, 393.2 K, 500 MHz) for the polymer samples A2 and M1.
The spectra exhibit peaks for vinyl acetate and ethylene as well as
additional peaks in the alkyl region (0.5-1.5 ppm) indicative of
the long alkyl chains on the branched vinyl ester monomer.
The .sup.1H NMR spectrum (TCE-D.sub.2, 393.2 K, 500 MHz) for A2 and
M1 are shown with a number of relevant peak assignments. FIG. 2
shows that there is overlap between vinyl acetate and the branched
vinyl ester monomer units around the peaks slightly upfield from 5
ppm. If these peaks were purely the methine of ethyl acetate, the
integral ratio between the 5 ppm peaks and the peak around 2 ppm
(methyl from vinyl acetate) would be 1:3. However, the integral
ratio is 1:1, indicating that the methines of both vinyl acetate
and branched vinyl ester overlap, generating the broadened peaks
around 5 ppm. Relative intensity of the peaks found in .sup.1H NMR
and .sup.13C NMR spectra are used to calculate monomer
incorporation of vinyl ester and VeoVa.TM. 10 in the
co-/terpolymers.
With particular respect to FIG. 3, the full .sup.13C NMR spectra
(TCE-d.sub.2, 393.1 K, 125 MHz) for samples E1 and E2 are shown.
There is evidence of incorporation of the trimethylsilyl-protected
methyl vinyl glycolate seen in the 175 ppm, 125 ppm and 50 ppm
regions. General peak assignments are also shown in FIG. 3.
Further evidence of the incorporation of the
trimethylsilyl-protected methyl vinyl glycolate monomer is
demonstrated in FIG. 4 showing the .sup.1H NMR spectra
(TCE-d.sub.2, 393 K, 500 MHz) for the polymer samples E1 and E2.
The spectra exhibit peaks for vinyl acetate and ethylene as well as
additional peaks (1.8 ppm and 3.8 ppm) indicative of the
trimethylsilyl-protected methyl vinyl glycolate monomer.
With particular respect to Table 1, a broad range of conversions
are obtained for each polymer. The degree of conversion during
polymerization will affect the degree of branching and topology of
the chains, altering properties of the polymers.
With particular respect to FIG. 5, a gel permeation chromatograph
is shown for the samples, from which the molecular weights and
distributions of the terpolymers were derived. The GPC experiments
were carried out in a gel permeation chromatography coupled with
triple detection, with an infrared detector IR5 and a four bridge
capillary viscometer, both from PolymerChar and an eight angle
light scattering detector from Wyatt. It was used a set of 4
column, mixed bed, 13 .mu.m from Tosoh in a temperature of
140.degree. C. The conditions of the experiments were:
concentration of 1 mg/mL, flow rate of 1 mL/min, dissolution
temperature and time of 160.degree. C. and 90 minutes, respectively
and an injection volume of 200 .mu.L. The solvent used was TCB
(Trichloro benzene) stabilized with 100 ppm of BHT.
The polymers A1-A5 containing VeoVa.TM. 10 exhibit molecular
weights ranging for 10 to 30 kDa and MWD around 2. Similar MWD is
observed for polymers B1-B3 and E1-E2. While the traces of the
terpolymers are similar to that of the comparative commercial
samples (M1-M3), they differ in their molecular weight
distribution, the commercial grades show a broader range of
molecular weights with MWD ranging from 4-6. However, depending on
the amount of comonomer incorporated, samples produced under
high-pressure conditions (polymers D1-D15 and E3-E4) show a broad
range of MWDs from about 2 to 31. Copolymers and terpolymers
produced under low-pressure conditions usually exhibit number
average molecular weights 1 to 300 kDa, weight average molecular
weights of 1 to 1000 kDa and MWDs of 1 to 60. On the other hand,
copolymers and terpolymers produced under high-pressure conditions
typically show number average molecular weights of 1 to 10000 kDa,
weight average molecular weights of 1 to 20000 kDa and MWDs of 1 to
60. Due to presence of high molecular weight chains in these
polymers, they can show unique properties compared to their low MWD
counterparts (such as higher melt strength, ESCR, impact strength,
etc.).
With particular respect to FIGS. 6A-6C, two-dimensional liquid
chromatography (2D-LC) chromatographs of polymers D13-D15 are
respectively shown. The 2D-LC system analyzed these copolymer and
terpolymers using high performance liquid chromatography (HPLC) and
GPC instruments. 2D-LC measurements were performed using a
PolymerChar 2D-LC high-temperature chromatograph (Valencia, Spain).
The instrument was equipped with a Hypercard.TM. HPLC column
(100.times.4.5 mm L.times.I.D., 5 .mu.m particle size) and a PLgel
Olexis GPC column (300.times.7.5 mm L.times.I.D., 13 .mu.m particle
size). The sample loop for 2D-LC contains a volume of 200 .mu.L.
All experiments were performed at 160.degree. C. Detection was
realized with a fixed wavelength infrared (IR) detector (IR6,
PolymerChar), with detection capabilities (bandpass filters) for
overall polymer concentration, CH2, CH3 and C.dbd.O. GPC elution
times were calibrated with polystyrene (EasiCal PS-1, Agilent,
Waldbronn, Germany). The calibration was performed in GPC mode and
applied to 2D-LC results as well. HPLC mobile phase was 1-decanol
(Merck, Darmstadt, Germany)/1,2-dichlorobenzene (ODCB, Acros
Organics, Schwerte, Germany), with a flow rate of 0.01 mL/min.
Gradient conditions: 0-200 min: pure 1-decanol, 200-700 min: linear
gradient of 1-decanol to ODCB, 700-1100 min: pure ODCB. Afterwards,
the column was flushed with 1-decanol at 0.8 mL/min for 40 min to
reestablish the adsorption equilibrium. GPC mobile phase was
1,2-dichlorobenzene (ODCB, Acros Organics, Schwerte, Germany) with
a flow rate of 1.5 mL/min. HPLC eluent from the fractionation valve
sample loops (100 .mu.L) was injected into the GPC every 10 min.
Sample concentrations were approximately 8 mg/mL, 6 mL mobile phase
were automatically added to the sample vials (containing weighed
polymer) by the autosampler, while simultaneously flushing them
with nitrogen. The samples were dissolved for 1 h, under shaking,
prior to injection. For calibration of HPLC elution times of EVA,
EVA samples with average vinyl acetate contents of 70, 50, 30, 14
and 5 wt % were used. All samples were mixed (similar
concentration, ca. 2 mg) and analyzed in a single 2D-LC run. For
calibration of HPLC elution times of VeoVA, a similar approach with
samples D1-D6 was used. Except for the low molecular weight
fraction, all polymers show a uniform distribution of vinyl acetate
and VeoVa.TM. 10 over the molar mass distribution. Concentration of
vinyl acetate and VeoVa.TM. 10 in the polymer chains varies between
10 to 65 wt % in these polymers.
To analyze the long chain branching frequency (LCBf) the samples
were analyzed using a GPC instrument equipped with IR5 infrared
detector and a four-capillary viscometry detector, the results of
which are shown in Table 2.
TABLE-US-00002 TABLE 2 Summary of LCBf Results Samples g' g B.sub.n
LCBf D5 0.715 0.620 8.048 1.284 D6 0.663 0.556 11.426 1.117 D7
0.878 0.830 2.173 0.547 D8 0.852 0.795 2.815 0.717 D10 0.927 0.897
1.155 0.334 D12 0.934 0.907 1.020 0.318 D14 0.948 0.926 0.787 0.270
D15 0.853 0.797 2.779 0.634
The content of long chain branching on several polymer samples was
measured .sup.13CNMR and the method described herein, the results
of which are summarized in Table 3 below.
TABLE-US-00003 TABLE 3 Summary of LCB Content Results Samples
B.sub.6+ D1 1.725 D5 1.010 D7 1.065 D10 1.338 D12 1.973 D14 1.312
D15 1.182
Thermal property analysis of the polymers was carried out using
Differential Scanning calorimetry (DSC), and Dynamic Mechanical
Analysis (DMA). With particular respect to FIG. 7A-7C, DSC analysis
of EVA and terpolymer samples is shown in FIG. 7A, where FIGS.
7B-7C provide an expanded view of the peaks in FIG. 7A. During DSC
analysis, these samples were equilibrated at 140.degree. C. for 5
min and the measurement proceeded at a cooling rate of 10.degree.
C./min followed by equilibration at -50.0.degree. C. and a heating
rate of 10.degree. C./min up to 140.degree. C.
Table 4 summarizes the DSC and DMA data. When comparing the
polymers containing the branched vinyl ester comonomer with the
comparative samples, the crystallization temperature appears most
affected from the incorporation of branched vinyl ester comonomers.
This trend is expected from the crystallization interruption caused
by the branched groups arising in the polymer from introduction of
the vinyl ester comonomers. Introduction of vinyl carbonyl
comonomers into a copolymer of ethylene and vinyl acetate may
result in a terpolymer with a different morphology from EVA
copolymers. This monomer may disrupt the structural regularity and
the polymer's ability to pack into a crystalline state.
Consequently, by increasing the amorphous regions the T.sub.g,
T.sub.m and T.sub.c of the obtained polymer may decrease.
Heat of crystallization (.DELTA.H), crystallization temperature,
melting temperature for polymers made in Examples 1 to 3 and
commercial EVA samples is shown in Table 4. The analyses were
carried out under nitrogen in a TA Q2000 instrument. A sample was
heated to 160.degree. C. at 10.degree. C./min, held at this
temperature for 1 minute, cooled down to -20.degree. C. at
10.degree. C./min and held at this temperature for 1 minute. Then,
the sample was heated up to 160.degree. C. at 10.degree. C./min.
The cooling and second heating curves were recorded, analyzed by
setting the baseline endpoints and the crystallization peak
temperature, melting peak temperature and .DELTA.H were
obtained.
TABLE-US-00004 TABLE 4 DSC, DMA, MFI and Density results for
Example 1, 2 and 3 Endothermic Den- T.sub.c peak T.sub.m peak
.DELTA.H MFI sity Samples (.degree. C.) (.degree. C.) (J/g) Tg
(.degree. C.) (g/10 min) (g/cm.sup.3) A1 46 70 12.4 -24 -- -- A2 40
66 9.9 -25 -- -- A3 31 51 1.5 -34 -- -- A4 34 59 1.6 -35 -- -- A5
36 58 6.3 -41 -- -- B1 44 63 19.9 -17 -- -- B2 43 56 17.2 -24 -- --
B3 18 39 10.7 9.2 -- -- D1 100 111 140 50 to -5 -- -- D2 99 112 136
50 to -10 -- -- D3 95 107 123 47 to -10 -- -- D4 92 106 117 45 to
-15 -- -- D5 83 97 97 50 to -20 -- -- D6 79 93 83 -20 -- -- D7 67
84 69 -24 -- -- D8 63 80 62 -24 -- -- D9 62 78 61 -23 -- -- D10 58
75 57 -22 -- -- D11 59 76 63 -21 -- -- D12 53 72 60 -20 26.5 -- D13
74 90 96 -18 118 0.9129 D14 60 77 64 -22 150 0.9290 D15 57 75 56
-16 95 0.9321 M1 52 73 19.2 -19 -- -- M2 53 74 21.9 -20 -- -- M3 86
101 113 6.3 -- --
Glass transition temperature (T.sub.g) for the samples were
determined from the measurement of Tan .delta. peak maximum of the
samples during DMA measurements using a TA 800 DMA instrument in
the tensile mode. Thin films made of each samples were cooled to
-150.degree. C. and their viscoelastic response was evaluated
through temperature sweep with a rate of 3.degree. C./min while a
preload force of 0.01 N with a frequency of 1 Hz and amplitude of
30 .mu.m was aplied. Storage modulus, loss modulus, and tan .delta.
(ratio of storage to loss modulus) was recorded as a function of
temperature. A reference temperature of 0.degree. C. was selected
to compare the storage modulus of the samples. In the range of
-75.degree. C. to 75.degree. C. the samples showed one to two
maximums in the tan .delta. versus temperature plot. In the case
where there is one peaks in the range of -75.degree. C. to
75.degree. C., it is designated as the .alpha. peak. In the case
where there is two peaks in the range of -75.degree. C. to
75.degree. C. , the maximum at higher temperature is designated as
the .alpha. relaxation while the maximum at the lower temperature
is marked as the .beta. relaxation. Different polymer morphology is
also discernible in DMA results. With particular respect to FIGS.
8A-8B, DMA of D2-D7, D9, and D11 are shown. D2-D6 show a broad
relaxation from -50 to 75.degree. C. By increasing the amount of
branched vinyl ester comonomer, the intensity of the .alpha.
relaxation peak decreases while the intensity of the .beta.
relaxation peak increases. D4 shows the broadest relaxation in this
region. Similar to commercial EVA samples, samples D7, D9, and D11
show single relaxation in this range.
With particular respect to Table 4, copolymers and terpolymers
produced in the Examples also show a broad range of MFR and
densities. Table 5 summarizes the storage modulus results at
0.degree. C. for Example 3, which depending on different
morphologies, cover a broad range of values.
TABLE-US-00005 TABLE 5 Storage modulus results for Example 3
Samples Storage Modulus at 0.degree. C. (MPa) D1 582 D2 465 D3 366
D4 354 D5 191 D6 76 D7 40 D8 33 D9 31 D10 26 D11 43 D12 26
Thermal degradation of the polymers was studied by thermal
gravimetric analysis (TGA) under a nitrogen atmosphere. The sample
is place in a TA Q500 TGA instrument and heated from 25 to
700.degree. C. with heating rate of 20.degree. C./min. Weight loss
as a function of temperature is recorded. With particular respect
to FIG. 9A-9B, TGA of D7-D10 is shown. All these polymers contain
about 30 wt % comonomers. The first weight loss in thermogram of
these polymers (at lower temperatures) is related to separation of
acidic groups (acetic acid or versatic acid) from the polymer. The
second weight loss at higher temperatures corresponds to
degradation of the polymer backbone. Replacing vinyl acetate with
VeoVa.TM. 10 during high pressure polymerization leads to polymers
that are more stable and show less weight loss at lower
temperatures. FIG. 9B shows that as the amount of VeoVa.TM. 10 in
the copolymers and terpolymers increases, the intensity of the
first weight lost (ratio of the amount of first weight loss divided
by the total comonomer content) decreases and the copolymer and
terpolymers become more thermally stable. The second degradation
occurs after 400.degree. C., where the carbon-carbon bonds in the
polymer backbone begins to degrade.
Samples were also subjected to thermal fractionation. Thermal
fractionation employs a temperature protocol (a series of heating
and cooling cycles) to produce a distribution of lamellar crystals
whose sizes reflect the distribution of methyl sequence lengths in
the copolymers and terpolymers. The thermal fractionation was
carried out in a TA Instruments Discovery DSC 2500, under nitrogen.
All cooling cycles were carried out at 5.degree. C./min and heating
cycles were carried out at 20.degree. C./min. Samples were heated
from 25.degree. C. to 150.degree. C., held at 150.degree. C. for 5
min, cooled to 25 C..degree. and held at this temperature for 3
min. The sample was subsequently heated to the first annealing
temperature (140.degree. C.), held at this temperature for 5 min
and cooled to 25.degree. C. The sample was heated again to the next
annealing temperature (130.degree. C.), held at this temperature
for 5 min and cooled to 25.degree. C. The procedure was repeated
until the last annealing temperature (70.degree. C.), in steps of
10.degree. C. Then, the sample was heated to 150.degree. C., at
20.degree. C./min in order to obtain the melting profile. Annealing
temperatures include: 140.degree. C., 130.degree. C., 120.degree.
C., 110.degree. C., 100.degree. C., 100.degree. C., 90.degree. C.,
80.degree. C. and 70.degree. C. The thermal fractionation by SSA
results in FIGS. 10A-10B.
Although only a few example embodiments have been described in
detail above, those skilled in the art will readily appreciate that
many modifications are possible in the example embodiments without
materially departing from this invention. Accordingly, all such
modifications are intended to be included within the scope of this
disclosure as defined in the following claims. In the claims,
means-plus-function clauses are intended to cover the structures
described herein as performing the recited function and not only
structural equivalents, but also equivalent structures. Thus,
although a nail and a screw may not be structural equivalents in
that a nail employs a cylindrical surface to secure wooden parts
together, whereas a screw employs a helical surface, in the
environment of fastening wooden parts, a nail and a screw may be
equivalent structures. It is the express intention of the applicant
not to invoke 35 U.S.C. .sctn. 112(f) for any limitations of any of
the claims herein, except for those in which the claim expressly
uses the words `means for` together with an associated
function.
* * * * *